Gray azo dyes.



CARL HAGEMANN, OF LEVERKUSEN, NEAR COLOGNE, GERMANY, ASSIGNOR T0 SYNTHETIC PATENTS C0,, INC., 0]? NEW YORK.

NEW YORK, N. Y., A CORPORATION or GRAY AZO DYES.

Specification of Letters Patent.

Patented June 25, 1918.

No Drawing. Application filed November 27, 1914, Serial No. 874,216. Renewed April 16, 1918. Serial No. 228,978.

To all whom it may concern:

Be it known that I, CARL HAGEMANN, doctor of philosophy, chemist, citizen of the German Empire, residing at Leverkusen, near Cologne, Germany, have invented new and useful Improvements in Gray Azo Dyes, of which the following is a specification.

I havefound that new and valuable trisazodyes dyeing cotton in general grayish shades can be produced by combining a diazocompound with a suitable middle component which can be further diazotized after copulation, rediazotizin and coupling with the same or another suc middle component, diazotizing and combining with one molecule of an aminonaphthol sulfonic acid, such as 2.8.6-, or 2.5.7 -aminonaphthol sulfonic acid, in a solution which is weakly acid or which contains bicarbonate. The new dyes are after being dried and pulverized in the shape of their alkali metal salts dark powders soluble in concentrated sulfuric acid generally with a reddish-gray to bluish to greenish coloration; yielding upon reduction with stannous chlorid and hydrochloric acid an aromatic aminocompound, diamins and an ortho-diaminooxynaphthalene sul; fonic acid. They dye cotton from reddishgray to greenish-gray shades fast to light.

As first components 6. g. the following can be used: 2-aminonaphthalene-4.8-disulfonic acid, 1naphthylamin-2-sulfonic acid, 2- naphthylamin-oor 8-sulfonic acids, anilin, sulfanilic acid, anisidins, xylidins, toluidins,

I iom acid an aromatic amino compound, diamins and an ortho-diamino-oxy-iraphthalene sulchloroanilins, nitranilins, chloroanilin sulfonic acids, chlorotoluidin sulfonic acids, aminosalicyl-ic acid, naphthylamins and their sulfonic acids, and as middle com ponents e. g. alpha-naphthylamin', 1.6- or 1.7 naphthylamin sulfonic acid, cresidin, anisidin, xylidin, aminonaphtholethers or their sulfonic acids, etc.

In order to illustrate the new process more fully the following example is given, the parts bein by weight- 242 parts of 4.5-dichloroanifinQ-sulfonic acid are diazotized .with 6.9 parts of sodium nitrite and parts of hydrochloric acid. The diazocompound is then combined with 25 parts of 1-naphthylamin-6-sulfonic acid, the resulting dye is further diazotized and the diazoderivative is combined with 25 parts of 1- naphthylamin-7-sulfonic acid rediazotized and added to a solution of 26 parts of 2- amino-8-naphthol-6-sulfonic acid containing 10 parts of sodium bicarbonate (NaHCO The dye is salted out, filtered off and dried. It is after being dried and pulverized in the shape of its alkali metal salt a dark powder soluble in concentrated sulfuric acid with a grayish coloration dyeing cotton gray shades fast to light. It yields upon reduction with stannous chlorid and hydrochloric acid 4.5-dichloroanilin-2-sulfonic acid, 1.4- naphthylenediamin sulfonic acid and 1.2-diamino-8-naphtho1-6-sulfonic acid. It has in a free state most probably the formula:

N=N k Ola fonic'acid dyeing cotton from reddish-gray to greenis -gray shades fast to light, substantially as described.

2. The herein described new trisazodyes Which'are after being dried and pulverized in the shape of their alkali metal salts dark powders soluble in concentrated sulfuric acid generally with a reddish-gray to bluish to greenish coloration yielding upon reduction with stannous chlorid and hydrochloric acid which are after being an aromatic amino sulfonic acid, diamins and an ortho-diamino-oxy-napththalene sulfonic acid; dyeing-cotton from reddish-gray to greenish gray shades fast to light, substantially as described.

3. The herein described new trisazodyes which are after being dried and pulverized in the shape of their alkali metal salts dark powders soluble in concentrated sulfuric acid generally with areddish-gray to bluish to greenish coloration yielding upon reduction with stannous chlorid and hydrochloric acid an aromatic amino sulfonic acid, diamins and a diamino-oxy-naphthalenesul fonic acid having the two amino-groups in the same ring; dyeing cotton from reddishgray to greenish-gray shades fast to light, substantially as described.

4. The herein described new trisazodyes.

which are after being dried and pulverized in the shape of their alkali metal salts dark powders soluble in concentrated sulfuric acid generally with a reddish-gray to bluish to greenish coloration yieldin upon reduction with stannous chlorid and ydrochloric acid an aromatic amino compound, diamins and a diamino oxy naphthalene sulfonic acid having two amino groups in the same ring; dyeing cotton from reddish-gray to greenish-gray shades fast to light, substantially as described.

5. The herein described new trisazodyes dried and pulverized in the shape of their alkali metal salts dark powders soluble in concentrated sulfuric acid generally with a reddish-gray to bluish to greenish coloration yielding upon reduction with stannous chlorid and hydrochloric acid an aromatic amino chloro sulfonic acid of the benzene series, diamins and a diaminooXy-naphthalene sulfonic acid; dyeing cotton from reddish-gray to greenish-gray shades fast to light, substantially as described.

6. The herein described new trisazodyes which are after being dried and pulverized in the shape of their alkali metal salts dark powders soluble in concentrated sulfuric acid generally with a reddish-grayv to bluish to greenish coloration yielding upon reduction with stannous chlorid and hydrochloric acid an aromatic amino compound, naphthyle'nediamin compounds and an orthodiamino-oxy-naphthalene sulfonic acid; dyeing cotton from reddish-gray to greenishwhich is after being dried and pulverized in' the shape of its alkali metal salt a dar greenish coloration yielding upon reduction with stannous chlorid and hydrochloric acid an aromatic amino compound, sulfonaphthylenediamins and diamino-oXy-napht-halene sulfonic acid; dyeing cotton from reddish-gray to greenish-gray shades fast to light, substantially. as described.

8. The herein described new trisazodyes which are after being driedand pulverized in the shape of their alkali metal salts dark powders soluble in concentrated sulfuric acid generally with a reddish-gray to bluish to greenish coloration yielding upon reduction wlth stannous chlorid and hydrochloric acid an aromatic amino compound, sulfonaphthy-' lenediamins and a diamino-oxy-naphthalen'e sulfonic acid having the two amino groups in the samering; dyeing cotton from reddish-gray to greenish-gray shades fast to 4 light, substantially as described.

9. The herein described new trisazodyes which are after being dried and pulverized in the shape of their alkali metal salts dark powders soluble in concentrated sulfuric acid generally with a grayish coloration I ieldin upon reduction with stannous c lorid and hydrochloric acid an amino-chloro-benzene sulfonic acid, aromatic diamins and a diamino-oXy-naphthalene sulfonic acid; dyeing cotton from grayish shades fast to light, substantially as described.

10. The herein described new trisazodyes which are after being dried and pulverized in the shape of their alkali metal salts dark powders soluble in concentrated sulfuric acid generally with a grayish coloration yielding upon reduction with stannous chloric and hydrochloric acid an amino-chlorobenzene sulfonic acid, sulfonaphthylene diamins and a diamino-oxy-naphthalene sulfonic acid neither of the amino groups being;

in ortho position to the oxy-group; dyeing cotton from grayish shades fast to light, substantiallyas described.

11. The herein described new trisazodye having in a free state most probably the formula:

pcwder soluble in concentrated sulfuric acid In testimony whereof I have hereunto setwith a grayish coloration; yielding upon remy hand in the presence of two subscribing l0 duction with sfannous chlorld and hydro- Witnesses.

'chloric acid 4.5dichloroanilin-Q-sulfonic 5 acid, 1.4-naphthylene-diamin sulfonic acid CARL HAGDMANN and 1.2-diamin0-8-naphthol-6-sulfonic acid; \Vitnesses: dyeing cotton grayish shades fast to light, J. WIJNEN,

substantially as described. J. C. ZIERECKEY. 

